Volume 44 (2013): Issue 3-4 (July 2013)

Agpaitic nepheline syenites have complex, Na-Ca-Zr-Ti minerals as the main hosts for zirconium and titanium, rather than zircon and titanite, which are characteristic for miaskitic rocks. The transition from a miaskitic to an agpaitic crystallization regime in silica-undersaturated magma has traditionally been related to increasing peralkalinity of the magma, but halogen and water contents are also important parameters. The Larvik Plutonic Complex (LPC) in the Permian Oslo Rift, Norway consists of intrusions of hypersolvus monzonite (larvikite), nepheline monzonite (lardalite) and nepheline syenite. Pegmatites ranging in composition from miaskitic syenite with or without nepheline to mildly agpaitic nepheline syenite are the latest products of magmatic differentiation in the complex. The pegmatites can be grouped in (at least) four distinct suites from their magmatic Ti and Zr silicate mineral assemblages. Semiquantitative petrogenetic grids for pegmatites in log a_Na2SiO5 - log a_H2O - log aHF space can be constructed using information on the composition and distribution of minerals in the pegmatites, including the Zr-rich minerals zircon, parakeldyshite, eudialyte, låvenite, wöhlerite, rosenbuschite, hiortdahlite and catapleiite, and the Ti-dominated minerals aenigmatite, zirconolite (polymignite), astrophyllite, lorenzenite, titanite, mosandrite and rinkite. The chemographic analysis indicates that although increasing peralkalinity of the residual magma (given by the activity of the Na₂Si₂O₅ or Nds component) is an important driving force for the miaskitic to agpaitic transition, water, fluoride (HF) and chloride (HCl) activity controls the actual mineral assemblages forming during crystallization of the residual magmas. The most distinctive mineral in the miaskitic pegmatites is zirconolite. At low fluoride activity, parakeldyshite, lorenzenite and wöhlerite are stable in mildly agpaitic systems. High fluorine (or HF) activity favours minerals such as låvenite, hiortdahlite,rosenbuschite and rinkite, and elevated water activity mosandrite and catapleiite. Astrophyllite and aenigmatite are stable over large ranges of Nds activity, at intermediate and low water activities, respectively.

Chevkinite-group minerals are widespread in a very wide range of igneous and metamorphic parageneses, forming important components of accessory mineral assemblages. Their presence in a rock may be difficult to establish by standard optical techniques, which has contributed to their importance being underestimated; a combination of SEM and EMPA is recommended here. Currently, there are eleven IMAapproved members of the group but undoubtedly several more will be described in the near future. There is considerable compositional variation in the group, which can be expressed as:

REE + M²⁺_C + M³⁺_C = Ca²⁺ _A + Sr + Ti⁴⁺_C + Zr⁴⁺_C

where A and C are structural sites. Chevkinite-group minerals strongly fractionate geochemically coherent pairs, such as LREE-HREE, Nb-Ta, Zr-Hf and Th-U, and thus play a critical role in geochemical modelling.

The Ukrainian Shield (USh) is a typical province of Proterozoic alkaline magmatism where about 50 massifs and occurrences of alkaline rocks and carbonatites have been found. In spite of the wide distribution of Devonian basaltic- and alkaline magmatic rocks in the Dnieper-Donetsk depression adjacent to the USh, and in a marginal zone of the USh adjacent to folded Donbass, only alkaline rocks of Proterozoic age (1.8-2.1 Ga) that have been identified in the central interior of the USh. Some discrete bodies of 2.8 Ga subalkaline rocks also occur in Bogdanivka massif (Azov area). Occurrences of both Proterozoic (prevailing) and Phanerozoic (Devonian) alkaline rocks and kimberlites are only found in the eastern part of the USh (Azov area). Kimberlites in the central part of the Ukrainian Shield (Kirovograd region) are also of Proterozoic age (ca 1.8 Ga). It is this predominance of Precambrian rocks that makes the USh so different from other alkaline provinces where Phanerozoic alkaline rocks and kimberlites commonly prevail over Precambrian rocks. The lack of Phanerozoic alkaline magmatism on USh is poorly understood.

Two main complexes of alkaline rocks - alkaline-ultrabasic (carbonatitic) and gabbro- syenitic - are distinguished in the USh. There are also rare occurrences of rock types such as alkaline- and alkaline-feldspar granites that may represent one separate alkaline-granite complex. Alkaline rocks present in the Eastern (Azov) province and in the Western province display essentially different geochemical character. Those of the Eastern province show characteristics typical of alkaline-ultrabasic rocks (e.g. high contents of incompatible rare elementssuch as Nb, REE, Zr, Y, Sr, whereas those in the Western province are characterized by low contents of Nb and Zr, and REE in some cases. This fact is interpreted as reflecting different geodynamic conditions of their origin. The Eastern rocks were formed in rift settings, the Western rocks in crustal compressional settings (collision, subduction). Various mineral deposits of phosphorus (apatite), niobium, REE, yttrium and zirconium, including unusually rich ores of REE, Y and Zr (Azov and Yastrybetsky) are associated with the alkaline rocks and carbonatites of the USh.

Baddeleyite as inclusions in zircon crystals is described for the first time from the ore zone of the Azov zirconium-rare-earth deposit in the Volodarsky (Pivdennokalchytsky) syenite Massif in the Ukrainian Shield. The main admixture in the zircon containing baddeleyite is hafnium (0.68 wt%). The baddeleyite occurs in a substance that fills cracks and that probably corresponds to glass. The chemical compositions of four baddeleyite segregations, and of the hosting glass, are presented. The baddeleyite formed as a result of interaction between zircon and silicate melt with a low SiO₂ content. The silicate melt formed under the influence of highthermobaric CO₂-fluid flows on the rock.